Conjugated diacetylenic dihydroperoxides



United States Patent CONJUGATED DIACETYLENIC DIHYDRO- PEROXIDES Nicholas A. Milas, Belmont, Mass.

N0 Drawing. Application July 9, 1953, Serial No. 367,078

Claims. (Cl. 260-610) In application Serial No. 248,090, filed September 24, 1951, now United States Patent No. 2,670,384, I have described a group of acetylene peroxides characterized by having at least one tertiary carbon atom having a peroxy group and an acetylenic group attached thereto.

I have now found that acetylenic peroxides of this group having two acetylenic linkages in conjugate relation are useful as catalysts in a wide .variety of polymerization reactions including polymerization reactions for the solidification of soils such as the polymerization of calcium acrylate in admixture with soils.

Although the new compounds of the invention are relatively stable under ordinary conditions they are highly sensitive to shock and can be easily detonated with a blasting cap. Owing to their unsaturation they have a very great potential energy and when exploded they have a much greater brisance than TNT.

The following specific examples are illustrative of the methods and products of the invention:

EXAMPLE 1 2,7-dimethyl-3,5-0ctadiyn-2,7-dihydroperoxide (I) CH3 CH1 CCEC EO-C CgCOH 0611 CH:

In to a cold (0) well-stirred mixture of hydrogen peroxide (85.5 g. of 48%) and sulfuric acid (144 g. of. 95.5%) in a tall 400 cc. beaker is added, in small portions, over a forty-five minute period, 50 g. (0.3 mole) of 2,7-dimethyl-3,5-octadiyn-2,7-diol, M. P. 131 C. The mixture is stirred at 0:5" C. for three hours longer, then diluted with an equal volume of a saturated solution of ammonium sulfate and extracted with ether. The ether extract is dried over magnesium sulfate, filtered and the ether removed under reduced pressure; yield of the crude peroxide, 53 g. This product recrystallized from glgitgr-esthagol mixtures gives crystalline peroxide, M. P.

EXAMPLE 2 3,8-dimethyl-4,6-decadiyn-3,8-dihydroperoxide (II) CH3 CH3 C-CEC-CEC-C CHaCfzCLOH 06H CHzCH:

Into a cold (0) well-stirred mixture of 14.2 g. (0.20 mole) of 48% hydrogen peroxide and 24.0 g. of 95.5% sulfuric acid is added 50 cc. of reagent grade benzene mixed with 10 cc. of anhydrous ethyl ether. The temperature is maintained at 5-10 C. and 2.35 g. (0.012 mole) of 3,8-dimethyl-4,6-decadiyn-3,S-diol, M. P. 73-76 C. (mixed isomers) is added in single portion. The temperature is kept below 10 C. for the first ten minutes, then allowed to rise to room temperature (25 C.). The whole mixture is stirred for one hour longer, after which time all solid has dissolved. An equal volume of saturated ammonium sulfate is then added, the mixture stirred for a little while longer and the benzene-ether layer separated. The non-aqueous layer is extracted once with saturated ammonium sulfate then neutralized with magnesium carbonate. Filtration and removal of the solvent under reduced pressure at room temperature 2,694,092 Patented Nov. 9, 1954 leaves 2.5 g. (91% yield) of a yellowish oil which analyzes for 12.0% active oxygen (85% of theory). Most of this oil crystallizes after standing 2-3 days at --4 C. By dissolving the oil in a small amount of benzene, adding a little pentane, and seeding in the cold (4 C.) with a crystal of the hydroperoxide, a colorless crystalline product is-obtained, M. P. 44-45.5 C.

EXAMPLE 3 7,7-dicyclohexyl-7,8-butadiyn-6,6-dihydr0per0xide (III) 0 OH O OH /CECCEC\ To a cold mixture, (0 'C.) of 14.2 g. (0.20 mole) of 48% hydrogen peroxide and 24 g. of 95.5% sulfuric acid is added a mixture of cc. benzene and 10 cc. anhydrous ether. The temperature is maintained at 5-10" C. To this mixture. is then added with rapid stir ring 4.92 g. (0.20 mole) of 7,7'-dicyclohexyl-7,8-butadiyn-diol-6,6', M. P. 173 C. The reaction temperature is then allowed to rise to room temperature (25 C.) and after one hour of stirring, the solid has completely dissolved. Stirring is continued for an additional hour,

then the non-aqueous layer is separated and washed with 96-97 C. (dec.).

EXAMPLE 4 2,4-hexadiyn-1,6-dihydroperoxide (TV) HOOCH2CEC-CECCH2OOH Into a cold (0 C.) well-stirred mixture of hydrogen peroxide (2.8 g. of 48%) and sulfuric acid (4.8 g. of 95.5%), 1.5 g. (0.014 mole) of 2,4-hexadiyndiol-1,6, M. P. 112-113", is added in small portions. Stirring is continued for three hours longer at 15 C., then the product is isolated in the manner followed under Examples 1, 2 and 3. When the ether is removed under reduced pressure a viscous oil (1.5 g.) is obtained which contains about 30% of the expected dihvdroperoxide. Attempts to purify this product bv crystallization have failed because of its relative instability.

The structure of the peroxides has been further established by complete hydrogenation and by infrared spectra.

I claim: 1. Coniu gated diacetylenic dihydroperoxides of the general formula and hydrocarbon chains forming a cvcloalkyl ring.

2. 2.7-dimethyl-3.5-octadivn-2.7-dihvdroperoxide.

3. 3.8-dimethyl-4.6-decadiyn-3,S-dihydroperoxide.

4. 7,7-dicyclohexy1-7,8'-butadiyn-6.6-dihydroperoxide. 5. 2,4-hexadiyn-1,6-dihydroperoxide.

References Cited in the file of this patent UNITED STATES PATENTS Name Da Number to Milas Feb. 23, 1954 

1. CONJUGATED DIACETYLENIC DIHYDROPEROXIDES OF THE GENERAL FORMULA 